Method of producing esters of cellulose



Patented Dec. 27, 1949 IVIETHOD OF PRODUCING ESTERS CELLULOSE George A. Richter, Jr., Springfield, Pa., assignor to American Viscose Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Original application March 16, 1944,

Serial No. 526,812. Divided and this application March 7, 1947, Serial No. 733,202

This application is a division of my pending application, Serial No. 526,812, filed March 16, 1944, now abandoned.

This invention relates to modified cellulose esters and more particularly to cellulose esters containing chemically bound radicals derived from agents which are capable of reacting bifunctionally with cellulose.

Cellulose fibers have an extremely high degree of plasticity which is accompanied by low elasticity, and tend to undergo irreversible flow under moderate stresses. Products molded from cellulose or its derivatives, such as cellulose esters, exhibit the same properties and tend to become deformed under stress, and this tendency is not reversed and the products do not revert to their original form when the stress is removed.

I have now prepared a series of modified cellulose esters which also contain chemically bound radicals derived from agents which are capable of reacting bifunctionally with cellulose, the properties of which are radically different from those of cellulose or unmodified esters thereof, in that in the new products the high degree of plasticity which is a distinguishing characteristic of cellulose or cellulose esters is modified in favor of a greatly enhanced elasticity.

The esters preferably contain from about one or less than one radical derived from the agent capable of reacting bifunctionally with cellulose per about 20 anhydro glucose units to one or less than one such radical per 500 anhydro glucose units or more. Of course, the ratio of the modifying radicals to glucose units may vary, but where the ratio is substantially higher than one in 20, the resulting product is extremely rigid and non-plastic.

In accordance with the invention, the radicals derived from agents capable of reacting bifunctionally with cellulose may be introduced simultaneously with or, in some cases, prior to the production of the esters.

According to one embodiment of the invention, at least one monobasic organic acid radical and at least one polybasic organic acid radical are introduced simultaneously into cellulose by reaction thereof with a monofunctional esterifying reagent and an esterifying agent capable of reacting bifunctionally with cellulose, the reaction being carried out in the presence of a substance in which the reaction product is at least partially solvated, that is, dissolved or swollen as it is formed during the reaction.

Suitable monofunctional reagents are monobasic organic acids, such as acetic, propionic,

6 Claims. (Cl. 260-225) butyric, lauric acids, etc., anhydrides of such acids, and acid halides derived therefrom.

Suitable bifunctionally reacting agents are such polybasic organic acids as adipic, succinic, sebacic acids, etc., as well as polyhalides of such acids.

Diacids derived from glycol, as well as dihalides thereof, such as compounds having the general formula XOCCHzCHz (OCI-IzCHz) nCHzCI-IzCOX where X is hydroxyl or halogen and n is any integer but preferably from 1 to 4, inclusive, may also be used. Such diacids derived from glycol may be prepared by the general procedure described by Bruson, Journal American Chemical Society 64, pages 2457 and 2850 In accordance with the invention, cellulose is simultaneously reacted with at least one polybasic organic acid, and at least one anhydride of a monobasic organic acid capable of esterifying cellulose, in the presence of a catalyst, which may be a mineral acid catalyst, for example, and a substance in which the reaction product is dissolved or swollen during the reaction. Alternatively, the cellulose may be simultaneously reacted with at least one monobasic organic acid, and at least one polybasic organic acid, in the presence of an impeller which may be an anhydride of a halogen-substituted monobasic or-" ganic acid, a catalyst, and a substance in which the reaction product is dissolved or swollen during the reaction.

Acid halides may also be used. Thus, the cellulose may be reacted simultaneously with at least one monobasic organic acid halide, and at least one polybasic organic acid halide, in the presence of a solvent or swelling agent for the reaction product and a condensing agent which is inert with respect to the halides, such as an organic base containing a nitrogen atom, all of the valences of which are attached to carbon, namely the tertiary amines of which pyridine, quinoline, and N-methyl morpholine are specifically named as examples.

According to another embodiment of the invention, introduction of the polybasic organic acid radicals may be effected, in some cases, prior to esterification of the cellulose with a monobasic organic acid. Thus, cellulose may be reacted with one or more diacids derived from glycol, or dihalides of such acids, in the presence of a condensing agent or catalyst, and the product thus obtained may then be subsequently reacted with at least one monobasic organic acid, in the usual manner.

An important feature of the invention is that the reaction is carried out in the presence of a substance in .which the .reaction product is dissolved or swollen as itissformed during the course of the reaction, which results in the reaction mass being maintained in a highly swollen or dissolved state and thus insures substantially uni-- form reaction between the cellulose and the monofunctional and bifunctional reagents. Such substances are for example, toluene, dioxane, acetone, etc. The final products which maybe obtained by precipitating the reaction mass from water, may be soluble or substantially insoluble in such substances.

The amount of monofuncti'onal reagent used may vary, but in general I prefer to use an amount thereof sufficient to form a tri-ester. If a more lowly esterified final product is desired, such as. a secondaryor monoester, the -tri-ester may be suitably hydrolyzed by conventional methods, aftercompletion of the reaction with the. bifunctionally reacting. esterification. agent.

By the .choice of ..bifunctional esterification agent and the amount thereof participating-in the .reaction, :it .is possible .to selectively adjust certainphysical properties of the final products, such as solubilities and softening temperatures. Although in all cases the modified esters show a lesserqdegreeof plasticityand a greater-degree of elasticity, and in general much higher softeningand melting temperatures and resistance to common solvents, as compared with corresponding :cellulose testers which -do not contain the modifying groups, modified esters .may also be obtained "which :do not greatly dilfer from the unmodified esters -.in'-r.espect-of solubility and softeningitemperatures. The degree to which the final modified esters are soluble in substances which-areisolvents for cellulose-esters, such as acetone, dioxane, toluene etc, forinstancemay vary, depending-upon the amountof bifunctional esterification agent used, greater amounts decreasing the solubility and lesser amounts increasing it. Thus, final products may be obtainedzwhich forms-smooth relatively clear solutionsiin :solvents such as.acetone,toluene, dioxane, etc or which form extremely viscous gel-like massestherein. Also, final. products maybe obtained which are insolublein'such common solvents or which :are merely swollen slightly when added thereto. Generally speaking, the" modified esters do not have melting points below-decomposition :-temperatures or sharp softening points, areasubstantially unaffected at temperatures "at Which the unmodified esters melt orsoften, do not show a tendency to soften iexcept within high temperature ranges, and at temperatures above the softening range are less plastic "and more-rubber-Jike than unmodifiedesters. However,'the softening temperature in-some instances may-'be'varied, depending upon the amount'and type-of i bifunctional esterification agent used, "the tendency :toso'ften' at relatively low temperatures being more marked in those cases where such agent isaused-in relatively small amounts and has a-longerchain-as comparedtothe ester side chain derived .from the monobasic acid; The use of marginal .amounts =.of :the bifunctional esterification agent. in the :reaction thus permits a :sensitive adjustment of the solubility and softening characteristicslof the end product. The amount of such agent to be used-depends uponthe properties zdesiredin .the final products. in general hydroxyl groups on parallel cellulose ch -masses which are, for the most part, insoluble,

infusible,.and heat-insensitive, but which in certain. cases, aspreviously indicated, may be soluble to varying extents :and more or less susceptible to softening by heat.

Some .of the insoluble or substantially insoluble .modified esters, such as cellulose butyrate containing sebacic acid radicals may be molded by compression and injection molding techniques to give molded articles which are characterized by hardness, resistance .to cold flow, and resistance to fiow atelevated temperatures. The molded products may undergo some flow under stress but :due .to their quality-of rapid and substantially complete elastic recovery, show a-lively return .to their'original form upon the removalof stress.

Those products which .are soluble insolvents such .as acetone, .for example, may be dissolved therein and extruded througha spinneret or the like .into an evaporative atmosphere, inaccordancewith-the dry-spinning process, toformar-tificialfilaments, or may be cast iromsuchsolutions .to give films,.sheets, coatings, etc., which areldurable and stable.

vIf .desired, substances may be :added to the products to .give various effects. Some of the substances which maybe added are suitablecoloring materials, such. as dyes, pigments, particles ofcoloredmaterials to givemottled effects, metallic particles .or the like.

The products exhibit properties such as a lesser degree of plasticity, greatly increased elasticity, generally increased softening and melting temperature .ranges,and range of solubility in commonsolvents which are-distinctly dlfierent from the properties of corresponding cellulose esters, such as-celluloselaurate, cellulose propionateetc, which do anot contain the chemically combined modifying pol-ybasic acid radicals. While the reasons for the marked change in. properties cannot'bestated precisely, it is believed that the change may be predicated upon a chemical -reaction of the polybasic acids or their halides with is, so that-crosselinks-are formed between the primary valence chains of the cellulose derivatives.

As' previouslyiindicated, the introduction of the radical or radicals derived from the bifunctional 1 esterificationragentmay'be effectedsiinultaneous- 1y with, or in some instances, prior tosubstantial esterification of the cellulose with the monobasic acids or their halides, when the-reaction is carried-ont in the presence of a solvent capable of swelling or dissolving the reaction product as it is formed'during the reaction. However, it has not been found practicable to effect chemical combination of the polybasicacid radicals'in the case-of pro-shaped cellulose'esters, and the more :highly .esterified the starting material 'thezgreatei' viously shaped partially-esterified cellulose, only Example I Five parts of air-dry wood pulp were suspended in a mixture of 50 parts of pyridine and 100 parts of toluene and the suspension was heated to 70- 80- C. A solution of 0.1 part of adipyl chloride in toluene was added to 40 parts of lauroyl chloride. The mixture was added dropwise to the above suspension, and the whole was heated to 75-85 C. for 4 hours. After precipitating and leaching with water, the reaction product (yield: 75% based on trilaurate) was obtained as a fibrous white mass which was substantially insolubleintoluene, did not soften below 140 C., and had no melting point. Unmodified cellulose laurate prepared under similar conditidns softened at about 65 C.

Example II The reaction was carried out in accordance with the procedure described in Example I, except that a 5% solution of 0.1 part of sebacoyl chloride were added to 40 parts of lauroyl chloride, and that mixture was added dropwise to the wood pulp suspension. After precipitating and leaching with water the reaction product (yield: 87% based on' tri-laurate) was obtained as a fibrous white mass which was insoluble in toluene, did not soften below 210 C., and had no melting point.

Example III 1 Eight parts of air-dry wood pulp were suspended in a mixture of 80 parts of pyridine and 100 parts of dioxane, and the suspension was heated to 60 to 80 C. A 5% solution of 0.06 part of sebacoyl chloride in toluene was added to 32 parts of butyryl chloride, and that mixture was added dropwise, with constant stirring, to the suspension. The mixture was heated to 15-85" C. for 2%; hours. The reaction product (yield:

83% based on tri-butyrate) was precipitated and leached with water and a fibrous white mass was obtained, which was insoluble in acetone, and had a softening range of 130-135 C. The softening range of unmodified cellulose butyrate prepared under similar conditions was found to be 125 130 C.

Example IV in a mixture of 50 parts of pyridine and 80 parts of dioxane and the suspension was heated to 60-985 C. A mixture of 26 parts of caproyl chlo-v ride and 0.08 part of succinyl chloride was added dropwise to the above suspension, and the whole was heated at -85" C. for about 3 hours. precipitating and leaching with water, the product was obtained as a white fibrous mass (yield: about 66% based on tricaproate). The product formed a very stiff gel in dioxane, and had a softening range of 120-130 C. Unmodified cellulose caproate prepared under similar conditions softened at about C.

Example VI Five parts of air-dry wood pulp were suspended in a mixture of 80 parts of pyridine and 100 parts of dioxane, and the suspension was heated to 60-430 C. 0.2 part of hexaglycol diacid chloride was mixed with 28 parts of propionyl chloride, and added dropwise to the wood pulp suspension: the mixture was kept at IS- C. for 3 hours.

After precipitating and leaching with water the:

final product (yield: 97% based on tri-propionate) occurred in the form of a white mass which was soluble in acetone, had a softening range of 155-l60 C., and could be drawn to coarse filaments at about 200 C.

Example VII had, softening range of l55l60 C. Unmodified cellulose propionate softened at about 155 C.

Example VIII Five parts of air-dry wood pulp were suspended in a mixture of 80 parts of pyridine and 100 parts of dioxane, and the suspension was heated to (SO-80 C. A mixture of 0.55 part of pentaglycol diacid chloride and 10 parts ofpropionyl chloride was added dropwise to the suspension. 18 parts of propionyl chloride were then :added and the mixture was heated at IS-85 C. for 2 hours. The product, after being leached with water, occurred in the form of a white, fibrous mass (yield: about 99% based on tri-propionate) which was soluble in acetone; had a softening range of -160" C., and which became rubber-like at 220-240 C.

Example IX The procedure was the same as described in Example VIII except that a mixture of 0.8 part of pentaglycol diacid chloride and 10 parts of propionyl chloride was added to the wood pulp suspension.

The final product (yield: 96% based on tri-propionate) was a white, fibrous mass which formed a grainy solution in acetone, and had a softening range of -165 0.

Example X The reaction was carried out in the manner described in Example VIII with the exception that a mixture of 1.12 parts of hexaglycol diacid chloride and 10 parts of propionyl chloride was added to the wood pulp suspension.

The product (yield: 76% based on tri-propio- After nate') was a fibrous white mass which "was soluble in acetone, had a softening range of about 1 601'65'1C., andbecame rubber like at 210-220" C...

Example XI About 10"par.ts of cotton linters were treated with a mixture ,of--;O,.5 part of sebacic acid dissolved :in 50 partsof glacial acetic acid for 2 hours at. SS-45 C. after which 115 parts of glacial acetic acid and 0.02 part of sulfuric acid were added. The temperature was maintained at about 38-45" C. for 'l 'hours, and then perniitted to drop to 30C., and maintained there for 1 hours. Thomas was cooled to 18 C. About 25.? parts of .acetic .acid' anhydride cooled to 30C. were added. The mass was then cooled to C., and :a mixture of 0.33 part of sulfuric acid "and "057 part of glacial acetic acid was stirred into the mass, and the'mixture was kept at C. for about 3 hours. Avery fibrous white mass was thus obtained. A mixture of 7 parts of sulfuric acid and '7 parts of "glacial acetic acid was added, to hydrolyze the'product to a secondaryacetate. 'The'hydrolyzed' material was placed I in a water bath at 40 C. ifor'24 hours. 'The 'mass was thinned with a little-acetone and precipitated by stirring in water; the precipitate was washed and dried. The product did not have a melting point below decomposition; had a softening range of about 230-235" -C., and was insoluble in acetone.

'The above examples and description are given byway of illustration, and modifications or variations may be made therein without departing from the spirit and scope of the invention as defined in the claims.

I 'claim:

1. The process comprising simultaneously reacting cellulose with at least one monobasic organic acid halide and at least one polybasic organic acid halide, lin -the presence of an organic base containing a nitrogen atom all of the valences of which are attached to carbon, and a substance in which the reaction product is at least partially solvated during the reaction.

2, The process comprising simultaneously reacting cellulose with at least one polybasic organic acid halide of'the general formula:

where n is an integen'and Ha is halogen, and at least one monobasic organic acid'halide, in

during the reaction.

3. The process comprising simultaneously 'racting cellulose with a suiiicient amount of' at least one monobasic organic acid halid'e'to form substantially a tri-estenandwith at least one polybasic organic acid halide, in the presenceof an organic base containing a nitrogen atom all of the valences of whichare-attached to carbon, and a substance in which the reaction product is at least partially'solvated during the reaction, terminating the reaction when substantially a monobas-ic acid 'tri-ester has been formed, and

hydrolyzing the tri-ester to a more *lowly-esterk fied product.

4. The process comprising simultaneously'reacting cellulose with at least one monobasic organic acid halide and at least one polybasic organic acid halide in the presence of an organic base containing a nitrogen atom all of the va lences of which are attached to carbon, and a substance in which the reaction product is at least partially solvated during the reaction, and terminating the reaction when substantially a monobasic acid tri-ester has been formed and the polybasic organicacidradicals have combined with the cellulose in a ratio of about one such radical per at least twenty anhydro-glucose units.

5. The process comprising simultaneously "reacting cellulose with sebacoyl dichloride and butyryl chloride, in the presence of pyridine and dioxane.

6. The process comprising simultaneously reactingcellulose with adipyl dichloride and lauroyl chloride'in the presence of pyridine'and toluene.

GEORGE A."RICHTER, JR.

REFERENCES CITED 'FQRE'IGN PATENTS Country Date Great Britain Sept. 27, 1928 OTHER REFERENCES Malm et .al., In. and Eng. Chem., 321405 to 408 (March 1940).

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